CN116529220A - Composition for forming optical fiber coating layer, cured layer thereof, optical fiber having cured layer, and use thereof - Google Patents
Composition for forming optical fiber coating layer, cured layer thereof, optical fiber having cured layer, and use thereof Download PDFInfo
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- CN116529220A CN116529220A CN202180077802.0A CN202180077802A CN116529220A CN 116529220 A CN116529220 A CN 116529220A CN 202180077802 A CN202180077802 A CN 202180077802A CN 116529220 A CN116529220 A CN 116529220A
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Abstract
Provided is a composition for forming a coating layer of an optical fiber, the composition comprising a compound having a structure represented by the following formula (I): (I) NH CO N (R) 1 )‑R 2 ‑SiR 3 n ‑(OR 4 ) 3‑n Wherein R is 1 Is a hydrogen atom, an alkyl group or an aryl group, R 2 C is a methylene group optionally substituted with halogen, an atomic group which may have a heteroatom between carbon atoms or a heteroatom, and may be optionally substituted with halogen 2‑10 Alkylene groups, orPhenylene group which may have substituent(s), R 3 Is an alkyl group, and R 4 Is C 1‑6 Alkyl groups, are bonds and n represents an integer of 0 or more and an integer of 2 or less.
Description
Technical Field
The present invention relates to a composition for forming a coating layer of an optical fiber and a cured layer thereof, an optical fiber having the cured layer and a method for producing the same, and use of the composition for forming a coating layer of an optical fiber.
Background
For the purpose of protection and reinforcement, optical fibers are produced by coating glass fibers that have been obtained by hot melt spinning of glass with a resin. Accordingly, a resin coating layer, that is, a structure obtained by first providing a soft first coating layer (hereinafter also referred to as "primary coating layer") on the surface of glass fiber and providing a high-rigidity second coating layer (hereinafter also referred to as "secondary coating layer") on the outer side of the first coating layer, is known. An optical fiber having a structure in which a primary coating layer and a secondary coating layer are provided on a single glass fiber is generally called an optical fiber bundle, and the optical fiber bundle may further have a colored ink layer or an upper jacket layer on the outer side of the second coating layer. In addition, ribbon fibers and fiber optic cables in which a plurality of such fiber bundles having a resin coating layer are fixed together with an adhesive material are also known.
The resin composition (coating material) for forming the first coating layer of the optical fiber bundle is referred to as a main material, the resin composition for forming the second coating layer is referred to as an auxiliary material, and the resin composition used as a bonding material of the plurality of optical fiber bundles is referred to as a bundling material. In addition, there are cases where a plurality of ribbon-like optical fibers and optical fiber cables are further bonded together by a bonding material, and the bonding material used in such cases is also called a bundling material. As the resin coating method in the above-described case, a method in which a liquid curable resin composition is applied and then cured by heat or light, particularly ultraviolet rays, is widely used.
Among these coating materials, the cured product of the main material must be flexible to prevent glass fibers from being bent or the like due to local pressure from the outside. For this reason, the primary coating layer generally has a Young's modulus of 0.1MPa to 10 MPa.
JP 2012-111674A discloses a radiation curable resin composition comprising a urethane oligomer and a monofunctional acrylic monomer as a resin composition suitable for use as a main material of an optical fiber bundle.
Disclosure of Invention
The object of the present invention is to obtain an appropriate glass adhesion strength while suppressing the change in Young's modulus after the main material has been cured due to an alkoxysilyl group-containing urethane oligomer. If the Young's modulus of the main material varies too much due to the alkoxysilyl group-containing urethane oligomer that has been blended into the main material, the transmission characteristics of the optical fiber become poor. Thus, such variations are undesirable.
Embodiments of the present invention include the following (1) to (25).
(1) A composition for forming a coating layer of an optical fiber, the composition comprising a compound having a structure represented by the following formula (I):
(I)*-NH-CO-N(R 1 )-R 2 -SiR 3 n -(OR4) 3-n
wherein R is 1 Is a hydrogen atom, an alkyl group or an aryl group, R 2 C is a methylene group optionally substituted with halogen, a radical which may have a heteroatom or contain a heteroatom between carbon atoms, and optionally substituted with halogen 2-10 An alkylene group, or a phenylene group which may have a substituent, R 3 Is an alkyl group, and R 4 Is C 1-6 Alkyl groups, are bonds and n represents an integer of 0 or more and an integer of 2 or less.
(2) The composition for forming a coating layer of an optical fiber according to (1), wherein R 1 Is a hydrogen atom or C 1-10 An alkyl group.
(3) The composition for forming a coating layer of an optical fiber according to (1) or (2), wherein R 2 C being a radical which may have heteroatoms or contain heteroatoms between carbon atoms 2-10 An alkylene group.
(4) The composition for forming a coating layer of an optical fiber according to any one of (1) to (3), wherein the hetero atom or hetero atom-containing atomic group is selected from the group consisting of NH, O and S.
(5) The composition for forming a coating layer of an optical fiber according to any one of (1) to (4), wherein R 3 Is C 1-10 An alkyl group.
(6) The composition for forming a coating layer of an optical fiber according to any one of (1) to (5), wherein R 4 Is C 2-6 An alkyl group.
(7) The composition for forming a coating layer of an optical fiber according to any one of (1) to (6), wherein the content of the compound having the structure represented by formula (I) is 0.05 parts by mass or more and less than 4.5 parts by mass per 100 parts by mass of the composition.
(8) The composition for forming a coating layer of an optical fiber according to (7), wherein the content of the compound having the structure represented by formula (I) is 0.4 parts by mass or more and less than 3 parts by mass per 100 parts by mass of the composition.
(9) The composition for forming a coating layer of an optical fiber according to any one of (1) to (8), wherein the compound having a structure represented by formula (I) is a urethane (meth) acrylate oligomer.
(10) The composition for forming a coating layer of an optical fiber according to (9), wherein the urethane (meth) acrylate oligomer contains a (meth) acrylate group.
(11) The composition for forming a coating layer of an optical fiber according to any one of (1) to (10), which further comprises a photopolymerization initiator.
(12) The composition for forming a coating layer of an optical fiber according to any one of (1) to (11), which further comprises a reactive diluent monomer.
(13) A cured layer formed from the composition for forming a coating layer of an optical fiber according to any one of (1) to (12).
(14) An optical fiber having the cured layer according to (13).
(15) An optical fiber ribbon or an optical fiber cable comprising two or more optical fibers according to (14).
(16) Use of a composition comprising a compound having a structure represented by the following formula (I):
(I)*-NH-CO-N(R 1 )-R 2 -SiR 3 n -(OR 4 ) 3-n
wherein R is 1 Is a hydrogen atom, an alkyl group or an aryl group, R 2 C is a methylene group optionally substituted with halogen, a radical which may have a heteroatom or contain a heteroatom between carbon atoms, and optionally substituted with halogen 2-10 An alkylene group, or a phenylene group which may have a substituent, R 3 Is an alkyl group, and R 4 Is C 1-6 Alkyl groups, are bonds and n represents an integer of 0 or more and an integer of 2 or less.
(17) The use according to (16), wherein R 1 Is a hydrogen atom or C 1-10 An alkyl group.
(18) The use according to (16) or (17), wherein R 2 C being a radical which may have heteroatoms or contain heteroatoms between carbon atoms 2-10 An alkylene group.
(19) The use according to any one of (16) to (18), wherein the heteroatom or heteroatom-containing radical is selected from NH, O and S.
(20) The use according to any one of (16) to (19), wherein R 3 Is C 1-10 An alkyl group.
(21) The use according to any one of (16) to (20), wherein R 4 Is C 2-6 An alkyl group.
(22) The use according to any one of (16) to (21), wherein the content of the compound having the structure represented by formula (I) is 0.05 parts by mass or more and less than 4.5 parts by mass per 100 parts by mass of the composition.
(23) The use according to (22), wherein the content of the compound having the structure represented by the formula (I) is 0.4 parts by mass or more and less than 3 parts by mass per 100 parts by mass of the composition.
(24) The use according to any one of (16) to (23), wherein the compound having a structure represented by formula (I) is a urethane (meth) acrylate oligomer.
(25) The use of any one of (16) to (24), wherein the urethane (meth) acrylate oligomer comprises a single (meth) acrylate group.
(26) The use according to any one of (16) to (25), which further comprises a photopolymerization initiator.
(27) The use of any one of (16) to (26), further comprising a reactive diluent monomer.
(28) A method for producing an optical fiber, the method comprising:
disposing the composition of any one of (1) to (12) on at least a portion of a surface of a glass fiber; and
the composition is cured to form a coating layer.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments and may be appropriately modified as long as the effects of the present invention are not hindered.
The composition for forming a coating layer of an optical fiber of an embodiment of the present invention is a composition for forming a coating layer of an optical fiber including a compound having a structure represented by the following formula (I) (hereinafter also referred to as "component (a)"):
(I)*-NH-CO-N(R 1 )-R 2 -SiR 3 n -(OR 4 ) 3-n 。
in formula (I), R 1 Is a hydrogen atom, an alkyl group or an aryl group. R is R 1 Preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. The alkyl group is preferably C 1-10 Alkyl groups, more preferably C 1-6 An alkyl group. The aryl group is preferably C 6-10 An aryl group.
In formula (I), R 2 Is a methylene group, has 2 or more andan alkylene group of 10 or less carbon atoms (hereinafter referred to as "C 2-10 "etc.) or phenylene groups which may have substituents. Examples of substituents for phenylene groups include halogen, hydroxy groups, C 1-6 Alkyl group and C 1-6 An alkoxy group. R is R 2 Preferably a methylene group or C 2-10 An alkylene group, more preferably C 2-6 An alkylene group. The above methylene group and alkylene group may be substituted with halogen, and the above alkylene group may have a heteroatom or a heteroatom-containing group between carbon atoms. Examples of the above-mentioned hetero atoms include oxygen atoms and sulfur atoms. Examples of the heteroatom-containing radical include NH. Examples of halogens include fluorine, chlorine and bromine.
In formula (I), R 3 Is an alkyl group, preferably C 1-10 Alkyl groups, more preferably C 1-6 An alkyl group.
In formula (I), R 4 Is C 1-6 An alkyl group, preferably C 2-6 Alkyl groups, more preferably C 2-4 An alkyl group.
Here, is a bond and n represents an integer of 0 or more and an integer of 2 or less, and n is preferably 0 or 1, more preferably 0.
Specific examples of the structure shown by formula (I) include, but are not limited to, the following structures.
Formula (IV) NH-CO-NH- (CH) 2 ) 3 -Si(OMe) 3
Formula (V): -NH-CO-NH- (CH) 2 ) 3 -Si(OEt) 3
The expression "primary coating of an optical fiber" is understood to mean a coating disposed at a position closest to the glass fiber among the coatings disposed on the glass fiber. The primary coating may be disposed to cover at least a portion of the surface of the glass fibers. The expression "primary coating for forming an optical fiber" is understood to mean a primary coating that can be used for forming an optical fiber, or for the purpose of forming a primary coating for an optical fiber.
The composition of the embodiment of the invention is particularly suitable for forming a primary coating layer (primary material) of an optical fiber.
The expression "urethane (meth) acrylate oligomer" is understood to mean an oligomer comprising in the molecule at least one (meth) acryl group in the repeating unit of the main chain and a urethane linkage (-NHCOO-). Urethane (meth) acrylate oligomers can generally be formed by: a reaction between the diol, the diisocyanate and the hydroxyl group-containing (meth) acrylate is induced, thereby forming a urethane bond. Useful diols, diisocyanates and hydroxyl group-containing (meth) acrylates are explained below.
The expression "having a structure of … …" is understood to mean a urethane (meth) acrylate oligomer having in its structure at least one structure represented by the above formula (I). Preferably, the structure of formula (I) is located at least one end of the backbone.
Component (a) is preferably a urethane (meth) acrylate oligomer. Hereinafter, the urethane (meth) acrylate oligomer as the component (a) is also referred to as "urethane oligomer (a)".
The urethane oligomer (a) preferably has a structure represented by formula (I) at least one end of the main chain, more preferably has a structure represented by formula (I) at only one end.
The diol forming a urethane bond in the urethane oligomer (a) is not particularly limited, but is preferably an aliphatic polyether diol. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polydecylene glycol, aliphatic polyether glycol obtained by ring-opening copolymerization of two or more types of ion-polymerizable cyclic compounds, and the like are preferable.
Examples of the above ion-polymerizable cyclic compounds include cyclic ethers such as ethylene oxide, propylene oxide, 1-butylene oxide, isobutylene oxide, 3-bischloromethyl oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxaoctane (tetraoxane), cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monoxide, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl epoxycyclohexane, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate.
Specific examples of polyether diols obtained by ring-opening copolymerization of two or more types of the above-mentioned ion-polymerizable cyclic compounds include binary copolymers obtained by a combination of tetrahydrofuran propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, and 1-butylene oxide and ethylene oxide; and a terpolymer obtained by a combination of tetrahydrofuran, 1-butylene oxide and ethylene oxide.
In addition, polyether diols obtained by ring-opening copolymerization of the above ion-polymerizable cyclic compounds with cyclic imines (e.g., ethyleneimine), with cyclic lactone acids (e.g., β -propiolactone or glycolic acid lactide), or with dimethylcyclopolysiloxane may also be used.
The above aliphatic polyether diol may be obtained, for example, as commercial products such as PTMG650, PTMG1000, and PTMG2000 (manufactured by Mitsubishi Chemical corp. Above); PPG400, PPG1000, PPG3000, and EXCENOL 720, 1020, and 2020 (manufactured by AGC inc. Above); PEG1000, universal DC1100, and DC1800 (manufactured by NOF CORPORATION, supra); PPTG2000, PPTG1000, PTG400, and PTGL2000 (manufactured by Hodogaya Chemical co., ltd. Above); z-3001-4, Z-3001-5, PBG2000A, PBG2000B, EO/BO4000, and EO/BO2000 (manufactured by DKS Co., ltd.); and Acclaim 2200, 2220, 3201, 3205, 4200, 4220, 8200, and 12000 (manufactured by Sumitomo Bayer Urethane co., ltd. Above).
Among these aliphatic polyether diols, from the viewpoint of achieving both high-speed applicability of the resin liquid and flexibility of the coating material, a diol which is a ring-opening polymer of one or more types of ion-polymerizable cyclic compounds having 2 to 4 carbon atoms and has an average molecular weight of 1,000 to 5,000 is preferably used. Examples of such preferred diol compounds include one or more ring-opening polymers selected from the group consisting of oxides of ethylene oxide, propylene oxide, 1-butylene oxide and isobutylene oxide, the ring-opening polymers having an average molecular weight of 1,000 to 4,000. Propylene oxide ring-opening polymers having an average molecular weight of 1,000 to 3,000 are particularly preferred.
Examples of the diisocyanate forming a urethane bond in the urethane oligomer (a) include aromatic diisocyanate, alicyclic diisocyanate, and aliphatic diisocyanate. Examples of the aromatic diisocyanate include 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3 '-dimethyl-4, 4' -diphenylmethane diisocyanate, 3 '-dimethylphenylene diisocyanate, 4' -biphenyl diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1, 3-phenyl diisocyanate, 4-diphenylpropane diisocyanate and tetramethylxylylene diisocyanate. Examples of cycloaliphatic diisocyanates include isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane. Examples of aliphatic diisocyanates include 1, 6-hexane diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Among the above, aromatic diisocyanates are more preferable from the viewpoint of economically obtaining a composition having stable quality, and 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate are particularly preferable. These diisocyanates may be used singly or in combination of two or more.
As the hydroxyl group-containing (meth) acrylate compound used in the synthesis of the urethane oligomer (a), it is preferable to use a hydroxyl group-containing (meth) acrylate in which a hydroxyl group is bonded to a primary carbon atom (referred to as a primary hydroxyl group-containing (meth) acrylate) and a hydroxyl group-containing (meth) acrylate in which a hydroxyl group is bonded to a secondary carbon atom (referred to as a secondary hydroxyl group-containing (meth) acrylate). (meth) acrylates containing primary hydroxyl groups are particularly preferred. Hydroxyl group-containing (meth) acrylates in which a hydroxyl group is bonded to a tertiary carbon atom (referred to as tertiary hydroxyl group-containing (meth) acrylates) are poor in reactivity with isocyanate groups (hereinafter also referred to as "NCO") and are therefore not preferred.
Examples of the primary hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolethane di (meth) acrylate.
Examples of the secondary hydroxyl group-containing (meth) acrylate include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 4-hydroxycyclohexyl (meth) acrylate. Examples also include compounds obtained by addition reaction of (meth) acrylic acid with glycidyl group-containing compounds such as alkyl glycidyl ethers, allyl glycidyl ethers and glycidyl (meth) acrylates.
The content of the urethane oligomer (a) in the composition for forming the coating layer of the optical fiber of the present invention is preferably 0.05 parts by mass or more and less than 10 parts by mass, more preferably 0.05 parts by mass or more and less than 5 parts by mass, even more preferably 0.05 parts by mass or more and less than 4.5 parts by mass, still more preferably 0.4 parts by mass or more and less than 4.5 parts by mass, particularly preferably 0.4 parts by mass or more and less than 3 parts by mass or 0.5 parts by mass or more and less than 3 parts by mass per 100 parts by mass of the composition. When the content of the urethane oligomer (a) is within these ranges, appropriate glass adhesion strength can be obtained while suppressing the change in young's modulus after the main material has been cured.
The urethane oligomer (a) is preferably synthesized by: a reaction between the diol component and the diisocyanate component is induced, and then a reaction between a compound having a structure represented by the following formula (II) and a hydroxyl group-containing (meth) acrylate is induced. As a result of such a reaction, a urethane oligomer having one or both ends terminated with a compound having a structure represented by formula (I) is preferably obtained. Urethane oligomers having one end capped with a compound having a structure represented by formula (I) are more preferable. When the ratio of the compound having the structure shown by the following formula (II) to the hydroxyl group-containing (meth) acrylate is adjusted as appropriate, a urethane oligomer having one end capped with the compound having the structure shown by the following formula (I) can be obtained.
(II)NH(R 1 )-R 2 -SiR 3 n -(OR 4 ) 3-n
The symbol R in the above formula (II) 1 、R 2 、R 3 、R 4 And n is defined as in formula (I), respectively.
Examples of the compound having a structure shown by the above formula (II) preferably include γ -aminopropyl trimethoxysilane and γ -aminopropyl triethoxysilane, and the compound is even more preferably γ -aminopropyl triethoxysilane.
In the synthesis of the urethane oligomer (a), a urethanization catalyst selected from copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, dioctyltin dilaurate, triethylamine, 1, 4-diazabicyclo [2.2.2] octane, 2,6, 7-trimethyl-1, 4-diazabicyclo [2.2.2] octane and the like is preferably used in an amount of 0.01% by mass to 1% by mass relative to the total amount of the reactants. Furthermore, the reaction is generally carried out at a reaction temperature of from 5℃to 90℃and particularly preferably from 10℃to 80 ℃.
In one embodiment, urethane (meth) acrylate oligomers other than component (a) may be blended into the composition used to form the coating layer of the optical fiber. Although there is no particular limitation on the urethane (meth) acrylate oligomer other than the component (a), as long as it is a urethane (meth) acrylate oligomer having no structure represented by the formula (I), examples thereof include urethane (meth) acrylate oligomers having two (meth) acryl groups in the molecule, urethane (meth) acrylate oligomers having one (meth) acryl group and one hydroxyl group in the molecule, and urethane (meth) acrylate oligomers having one (meth) acryl group in the molecule and one silicon-containing group other than those represented by the formula (I).
The urethane (meth) acrylate oligomer having two (meth) acryl groups in a molecule is, for example, a urethane (meth) acrylate oligomer obtained by inducing a reaction between a diol, a diisocyanate, and a hydroxyl group-containing (meth) acrylate.
Examples of urethane (meth) acrylate oligomers having one (meth) acryl group and one hydroxyl group in the molecule include urethane (meth) acrylate oligomers having one (meth) acryl group derived from a hydroxyl group-containing (meth) acrylate and one hydroxyl group derived from an alcohol.
Examples of urethane (meth) acrylate oligomers having one (meth) acryl group and one silicon-containing group other than those shown by the formula (I) in the molecule include urethane (meth) acrylate oligomers having one (meth) acryl group derived from a hydroxyl group-containing (meth) acrylate and a hydroxyl group derived from a silane coupling agent other than those shown by the formula (I). The silane coupling agent other than those represented by the formula (I) is preferably, for example, gamma-mercaptopropyl trimethoxysilane.
In one embodiment, a urethane oligomer having no (meth) acryl group in the molecule may also be blended into the composition for forming the coating layer of the optical fiber. The urethane oligomer having no (meth) acryl group in the molecule is, for example, a urethane oligomer obtained by inducing a reaction between a diol, a diisocyanate, and an alcohol. The alcohol is preferably a lower alcohol having 1 to 8 carbon atoms. For example, aliphatic alcohols such as methanol or n-octanol are preferred.
In one embodiment, a compound having one ethylenically unsaturated group (component (B)) other than component (a) may be blended into the composition for forming the coating layer of the optical fiber. Component (B) is generally a monomer having one ethylenically unsaturated group. Examples of the component (B) include aliphatic structure-containing (meth) acrylates, alicyclic structure-containing (meth) acrylates, aromatic structure-containing (meth) acrylates, vinyl group-containing lactams, and (meth) acrylamides.
Among these, examples of the aliphatic structure-containing (meth) acrylic acid esters as the component (B) include butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol (meth) acrylate, ethoxy ethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and methoxy polypropylene glycol (meth) acrylate.
Examples of the alicyclic structure-containing (meth) acrylate as the component (B) include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
Examples of the aromatic structure-containing (meth) acrylate as the component (B) include benzyl (meth) acrylate.
Examples of the vinyl group-containing lactams as component (B) include N-vinylpyrrolidone and N-vinylcaprolactam.
Examples of (meth) acrylamides as component (B) include diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N-dimethyl (meth) acrylamide and t-octyl (meth) acrylamide.
Examples of the component (B) include, in addition to the above-mentioned compounds, acryloylmorpholine, vinylimidazole and vinylpyridine; and examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl acrylate.
Of these components (B), aliphatic structure-containing (meth) acrylates such as 2-ethylhexyl (meth) acrylate and vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam are preferred.
In addition, examples of commercial products of the above component (B) include Aronix M-111, M-113, M-114 and M-117 (manufactured by TOAGOSEI CO., LTD. Above), KAYARAD TC110S, R629 and R644 (manufactured by Nippon Kayaku Co., ltd. Above), and IBXA and Viscoat 3700 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD. Above).
Component (B) is preferably blended in an amount of 5 to 45 mass%, particularly 10 to 30 mass%, relative to 100 mass% of the total amount of the liquid curable resin composition of the present invention. The component (B) is preferably blended in an amount of 5 parts by mass or more and 45 parts by mass or less, particularly 10 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the total amount of the composition of the present invention, in parts by mass.
In one embodiment, a compound comprising two or more ethylenically unsaturated groups (component (C)) may be blended into a composition for forming a coating layer of an optical fiber. Component (C) is generally a monomer comprising two or more ethylenically unsaturated groups. Component (B) and component (C) are sometimes referred to as reactive diluent monomers. Specific examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane (meth) acrylate, tri (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tri (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, di (meth) acrylate of diol of ethylene oxide or propylene oxide adduct of bisphenol a, di (meth) acrylate of diol of ethylene oxide or propylene oxide adduct of hydrogenated bisphenol a, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol a, and triethylene glycol divinyl ether. Further, examples of commercial products include yupin UV SA1002 and SA2007 (manufactured by Mitsubishi Chemical corp. Above); viscoat 700 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY ltd.); KAYARAD R-604, DPCA-20, DPCA-30, DPCA-60, DPCA-10, HX-620, D-310, and D-330 (manufactured by Nippon Kayaku Co., ltd.); and Aronix M-210, M-215, M-315, and M-325 (manufactured by TOAGOSEI CO., LTD. Above).
From the viewpoint of easy adjustment of the young's modulus of the cured product to a range favorable for use as a main material (material for forming a primary coating layer) of an optical fiber, the content of the compound having two or more ethylenically unsaturated groups is preferably 2 mass% or less (0 mass% to 2 mass%), more preferably 1.5 mass% or less (0 mass% to 1.5 mass%) with respect to the total amount of the resin composition. The amount of the component (C) is preferably 2 parts by mass or less (0 parts by mass to 2 parts by mass), more preferably 1.5 parts by mass or less (0 parts by mass to 1.5 parts by mass) relative to 100 parts by mass of the total amount of the composition, in parts by mass.
In photocuring the resin composition of the present invention, a photopolymerization initiator (component (D)) is used, and furthermore, a photosensitizer may be added as necessary. Here, examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4 '-dimethoxybenzophenone, 4' -diaminobenzophenone, michaelin ketone, benzoin propyl ether, benzoin diethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propane-1-one, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2, 4-trimethylamyl phosphine oxide; irgacure 184, 369, 651, 500, 907, CGI 1700, CGI 1750, CGI 1850, CG24-61, darocur 1116 and Darocur1173 (manufactured above by Ciba Specialty Chemicals co., ltd.); lucirin TPO (manufactured by BASF); and Ubecryl P36 (manufactured by UCB). Further, examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate; and Ubecryl P102, 103, 104, and 105 (manufactured by UCB above).
The photopolymerization initiator (D) is preferably blended in an amount of 0.1 to 10 mass%, particularly 0.3 to 7 mass%, relative to 100 mass% of the total amount of the liquid curable resin composition of the present invention. The photopolymerization initiator (D) is preferably blended in an amount of 0.1 parts by mass or more and 10 parts by mass or less, particularly 0.3 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the total amount of the composition, in parts by mass.
In one embodiment, the silane coupling agent may be blended into the composition for forming the coating layer of the optical fiber within a range that does not hinder the effect of the present invention. The silane coupling agent is not particularly limited, and vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β -methoxy-ethoxy) silane, β - (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, γ -glycidoxypropyl trimethoxysilane, γ -glycidoxypropyl methyldiethoxysilane, γ -methacryloxypropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl trimethyldimethoxysilane, N-phenyl- γ -aminopropyl trimethoxysilane, γ -chloropropyl trimethoxysilane, γ -mercaptopropyl trimethoxysilane, γ -aminopropyl trimethoxysilane, and the like can be used. In addition, bis- [3- (triethoxysilyl) propyl ] tetrasulfide, bis- [3- (triethoxysilyl) propyl ] disulfide, gamma-trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, gamma-trimethoxysilylpropyl benzothiazolyl tetrasulfide and the like can also be used. Examples of commercial products of these compounds include SH6062 and SZ6030 (manufactured by Dow Corning Toray Silicone co., ltd., above); and KBEs 903, 603, and 403 (manufactured by Shin-Etsu Chemical co., ltd., above). From the viewpoint of the adhesive strength between the coating layer and the glass, as these silane coupling agents, γ -glycidoxypropyl trimethoxysilane, γ -methacryloxypropyl trimethoxysilane, γ -mercaptopropyl trimethoxysilane and γ -aminopropyl trimethoxysilane are preferable. These silane coupling agents may be used alone or in combination of two or more.
From the viewpoint of maintaining the adhesive strength between the cured product and the glass fiber, the content of the silane coupling agent is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, and particularly preferably 0.5 to 1.5% by mass, relative to the total amount of the composition for forming the coating layer of the optical fiber. From the viewpoint of maintaining the adhesive strength between the cured product and the glass fiber, the content of the silane coupling agent is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.1 parts by mass or more and 1.5 parts by mass or less, particularly preferably 0.5 parts by mass or more and 1.5 parts by mass or less, relative to 100 parts by mass of the total amount of the composition.
In one embodiment, various types of additives such as antioxidants, colorants, ultraviolet absorbers, light stabilizers, thermal inhibitors, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, and coating surface improvers may be blended as needed in addition to the above components.
Examples of antioxidants include Irganox 245, 1010, 1035, 1076, and 1222 (manufactured by BASF Japan ltd., above); and anti-genes P and 3C and Sumilizer GA-80 and GP (manufactured by Sumitomo Chemical co., ltd.). Examples of the ultraviolet absorber include TINUVIN P, 234, 320, 326, 327, 328, 329, and 213 (manufactured by BASF Japan ltd. Above); and SEESORB 102, 103, 501, 202, 712, and 704 (manufactured by Shipro Kasei Kaisha, ltd. Above). Examples of light stabilizers include TINUVIN 292, 144, and 622LD, sanol LS-770 and 765 (manufactured by BASF Japan ltd, above); and TM-061 (manufactured by Sumitomo Chemical co., ltd.).
Further, although there is no particular limitation on the surfactant, a nonionic surfactant based on a fatty acid ester is preferable for effectively suppressing occurrence of defects when immersing the optical fiber bundle in hot water. Nonionic surfactants such as glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and polyoxysorbitol fatty acid esters are particularly preferable.
In one embodiment, other oligomers and polymers, silane compounds such as tetraethoxysilane (silane compounds other than the above-described silane coupling agents), other additives, and the like may be optionally blended into the composition for forming a coating layer of an optical fiber of the present invention within a range that does not hinder the effect of the present invention.
Examples of other oligomers and polymers include polyester (meth) acrylates, epoxy (meth) acrylates, polyamide (meth) acrylates, silicone polymers containing (meth) acryloxy groups, and glycidyl methacrylate.
The production method of the composition for forming the coating layer of the optical fiber is not particularly limited, and may be performed by melting and blending the components in a conventionally known reaction vessel equipped with a stirrer.
From the viewpoint of handling ability and applicability, the viscosity of the composition for forming the coating layer of the optical fiber at 25 ℃ is preferably 0.1Pa-s to 10Pa-s, more preferably 1Pa-s to 8Pa-s.
The cured layer formed from the composition for forming the coating layer of the optical fiber has a low young's modulus, which is advantageous for use as a primary coating layer of the optical fiber. From the viewpoint of being capable of being used well as a primary coating layer of an optical fiber, the Young's modulus of a cured product of a composition for forming a coating layer of an optical fiber is preferably 0.1MPa or more and 1.0MPa or less (0.1 MPa to 1.0 MPa) at 25 ℃ as a value 14 days after formation of the cured layer. If the Young's modulus of the cured layer formed of the composition for forming the coating layer of the optical fiber is 0.1MPa to 1.0MPa at 25 ℃, so-called microbending in which the glass fiber becomes bent when a local pressure is applied to the optical fiber can be prevented. The Young's modulus of the cured layer formed from the composition for forming the coating layer of the optical fiber is more preferably 0.2MPa or more and 0.9MPa or less (0.2 MPa to 0.9 MPa), even more preferably 0.3MPa or more and 0.85MPa or less (0.3 MPa to 0.85 MPa).
Young's modulus indicates a certain change over time after the cured film was formed. The variation in Young's modulus at 14 days after formation of the cured layer is preferably 0.05MPa or less, and even more preferably 0.04MPa or less. When the amount of change in Young's modulus is within this range, an optical fiber having more stable quality (having particularly excellent transmission characteristics) can be obtained.
As a value at 14 days after formation of the cured layer, the glass adhesion strength is preferably 40N/m or more and less than 85N/m, more preferably 50N/m or more and less than 70N/m, particularly preferably 50N/m or more and less than 65N/m. When the glass adhesive strength is within this range, even when localized pressure is applied to the optical fiber, the glass fiber and the cured film become difficult to separate, and an optical fiber with stable quality can be obtained. In addition, workability of peeling and removing the cured film as the coating layer is improved when performing the optical fiber connection work.
The glass bond strength indicates a certain change over time after the cured film is formed. The amount of change at 14 days after formation of the cured layer is preferably 15N/m or more and less than 60N/m, N/m, even more preferably 15N/m or more and less than 40N/m, particularly preferably 20N/m or more and less than 40N/m. When the amount of change in the glass adhesion strength is within this range, an optical fiber having more stable quality can be produced.
The composition for forming the coating layer of the optical fiber is preferably a composition exhibiting young's modulus and glass adhesion strength within the above-mentioned ranges. Further, when the change in young's modulus with time is within the above range, appropriate glass adhesion strength is provided while suppressing the change in young's modulus after curing, which is more preferable from the viewpoint of stability of optical fiber quality. In addition, a change with time of the glass adhesion strength is more preferable in the above range, and both a change with time of the young's modulus and a change with time of the glass adhesion strength are even more preferable in the above range.
An optical fiber including a cured layer of a composition for forming a coating layer of the optical fiber is provided with the cured layer of the composition for forming the coating layer of the optical fiber as a primary coating layer on the surface of a glass fiber. The optical fiber preferably includes a secondary coating layer in contact with the outside of the primary coating layer, the Young's modulus of the secondary coating layer being 1,000MPa or more, preferably 1,000MPa to 2,000MPa. A glass fiber having a primary coating layer and a secondary coating layer in this order on its surface can be used as the optical fiber bundle.
The production method for an optical fiber includes providing a composition for forming a coating layer of an optical fiber on at least a part of a surface of a glass fiber, and curing the composition for forming a coating layer of an optical fiber, wherein the composition for forming a coating layer of an optical fiber contains the composition for forming a coating layer of an optical fiber described above.
There is no limitation on the method of disposing the composition for forming the coating layer of the optical fiber on at least part of the surface of the glass fiber, and there may be involved applying the radiation polymerizable composition to the surface of the glass fiber, immersing the glass fiber in the composition for forming the coating layer of the optical fiber, and the like, according to conventionally known methods.
The method for curing the above-mentioned composition for forming the coating layer of the optical fiber by irradiation with radiation is not particularly limited, and relates to irradiation of the polymerizable composition with one or more types of radiation selected from infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like.
The production of optical fibers generally involves applying a primary material and a secondary material while thermally melting and drawing a molten quartz preform, and radiation curing the materials to form a primary coating layer and a secondary coating layer.
An aggregate such as an optical fiber ribbon or an optical fiber cable is an aggregate including two or more optical fibers including the cured layer of the above-described composition for forming a coating layer of an optical fiber, and the aggregate may be formed into a ribbon-like optical fiber or an optical fiber cable in which optical fibers are fixed together with an adhesive material.
Examples
The present invention will be described in more detail by referring to the following examples, but the present invention should not be construed as being limited to these examples.
Synthesis of urethane acrylates
Synthesis example 1
Synthesis example 1 of urethane acrylate (A)
A reaction vessel equipped with a stirrer was charged with 65.2g of polypropylene glycol having a number average molecular weight of 2,000, 7.57g of 2, 4-toluene diisocyanate and 0.0180g of 2, 6-di-t-butyl-p-cresol, respectively, and these components were heated while stirring until the liquid temperature reached 40 ℃. Next, after 0.0200g of dibutyltin dilaurate was added, the liquid temperature was raised to 60 ℃ over 10 minutes while stirring. Thereafter, each component was stirred for 60 minutes, and after the residual isocyanate group concentration became 1.17 mass% (ratio with respect to the charged amount) or less, 0.315g of gamma-aminopropyl triethoxysilane and 1.72g of 2-hydroxyethyl acrylate were added, and each component was reacted at a liquid temperature of 70 ℃ for 60 minutes. After the residual isocyanate group concentration became 0.313 mass% (relative to the charged amount) or less, 0.178g of methanol was added, and the components were reacted at a liquid temperature of 70℃for 60 minutes. When the residual isocyanate group concentration becomes 0.0500 mass% or less, the reaction is terminated.
The urethane oligomers obtained were three urethane oligomers "HT- (PPG 2000-T" shown in example 1 in Table 2 3 -H”、“HT-(PPG2000-T) 3 -NH-(CH 2 ) 3 -Si(OEt) 3 "He" HT- (PPG 2000-T) 3 Mixtures of OMe ".
In the urethane oligomer structure shown in table 2, "H" represents a hydroxyethyl acrylate residue, "T" represents a toluene diisocyanate residue, "PPG2000" represents a polypropylene glycol residue having a molecular weight of 2,000, "Me" represents a methyl group, and "Et" represents an ethyl group.
Synthesis example 2
Synthesis example 2 of urethane acrylate (A)
A reaction vessel equipped with a stirrer was charged with 65.4g of polypropylene glycol having a number average molecular weight of 2,000, 7.60g of 2, 4-toluene diisocyanate and 0.0180g of 2, 6-di-t-butyl-p-cresol, respectively, and these components were heated while stirring until the liquid temperature reached 40 ℃. Next, after 0.0200g of dibutyltin dilaurate was added, the liquid temperature was raised to 60 ℃ over 10 minutes while stirring. Thereafter, each component was stirred for 60 minutes, and after the residual isocyanate group concentration became 1.25 mass% (ratio with respect to the charged amount) or less, 0.0315g of gamma-aminopropyl triethoxysilane and 1.72g of 2-hydroxyethyl acrylate were added, and each component was reacted at a liquid temperature of 70 ℃ for 60 minutes. After the residual isocyanate group concentration became 0.386 mass% (relative to the charged amount) or less, 0.220g of methanol was added, and the components were reacted at a liquid temperature of 70℃for 60 minutes. When the residual isocyanate group concentration becomes 0.0500 mass% or less, the reaction is terminated.
The urethane oligomers obtained were three urethane oligomers "HT- (PPG 2000-T" shown in example 5 in Table 2 3 -H”、“HT-(PPG2000-T) 3 -NH-(CH 2 ) 3 -Si(OEt) 3 "He" HT- (PPG 2000-T) 3 Mixtures of OMe ".
Synthesis example 3
Synthesis example 3 of urethane acrylate (A)
A reaction vessel equipped with a stirrer was charged with 65.3g of polypropylene glycol having a number average molecular weight of 2,000, 7.58g of 2, 4-toluene diisocyanate and 0.0180g of 2, 6-di-t-butyl-p-cresol, respectively, and these components were heated while stirring until the liquid temperature reached 40 ℃. Next, after 0.0200g of dibutyltin dilaurate was added, the liquid temperature was raised to 60 ℃ over 10 minutes while stirring. Thereafter, each component was stirred for 60 minutes, and after the residual isocyanate group concentration became 1.25 mass% (ratio with respect to the charged amount) or less, 0.256g of gamma-aminopropyl trimethoxysilane and 1.72g of 2-hydroxyethyl acrylate were added, and each component was reacted at a liquid temperature of 70 ℃ for 60 minutes. After the residual isocyanate group concentration became 0.311 mass% (relative to the charged amount) or less, 0.178g of methanol was added, and the components were reacted at a liquid temperature of 70℃for 60 minutes. When the residual isocyanate group concentration becomes 0.0500 mass% or less, the reaction is terminated.
The urethane oligomers obtained were three urethane oligomers "HT- (PPG 2000-T" shown in example 8 in Table 2 3 -H”、“HT-(PPG2000-T) 3 -NH-(CH 2 ) 3 -Si(OMe) 3 "He" HT- (PPG 2000-T) 3 Mixtures of OMe ".
Comparative Synthesis example 4
Synthesis example 1 of urethane acrylate not corresponding to component (A)
A reaction vessel equipped with a stirrer was charged with 65.3g of polypropylene glycol having a number average molecular weight of 2,000, 7.58g of 2, 4-toluene diisocyanate and 0.0180g of 2, 6-di-t-butyl-p-cresol, respectively, and these components were heated while stirring until the liquid temperature reached 40 ℃. Next, after 0.0200g of dibutyltin dilaurate was added, the liquid temperature was raised to 60 ℃ over 10 minutes while stirring. Thereafter, each component was stirred for 60 minutes, and after the residual isocyanate group concentration became 1.25 mass% (ratio with respect to the charged amount) or less, 0.280g of γ -mercaptopropyl trimethoxysilane and 1.72g of 2-hydroxyethyl acrylate were added, and each component was reacted at a liquid temperature of 70℃for 90 minutes. After the residual isocyanate group concentration became 0.312 mass% (relative to the charged amount) or less, 0.178g of methanol was added, and the components were reacted at a liquid temperature of 70℃for 60 minutes. When the residual isocyanate group concentration becomes 0.0500 mass% or less, the reaction is terminated.
The urethane oligomers obtained were three urethane oligomers "HT- (PPG 2000-T" shown in comparative example 2 in Table 2 3 -H”、“HT-(PPG2000-T) 3 -S-(CH 2 ) 3 -Si(OMe) 3 "He" HT- (PPG 2000-T) 3 Mixtures of OMe ".
Comparative Synthesis example 5
Synthesis example 2 of urethane acrylate not corresponding to component (A)
A reaction vessel equipped with a stirrer was charged with 65.4g of polypropylene glycol having a number average molecular weight of 2,000, 7.59g of 2, 4-toluene diisocyanate and 0.0180g of 2, 6-di-t-butyl-p-cresol, respectively, and these components were heated while stirring until the liquid temperature reached 40 ℃. Next, after 0.0200g of dibutyltin dilaurate was added, the liquid temperature was raised to 60 ℃ over 10 minutes while stirring. Thereafter, each component was stirred for 60 minutes, and after the residual isocyanate group concentration became 1.25 mass% (ratio with respect to the charged amount) or less, 0.140g of gamma-mercaptopropyl trimethoxysilane and 1.72g of 2-hydroxyethyl acrylate were added, and each component was reacted at a liquid temperature of 70℃for 90 minutes. After the residual isocyanate group concentration became 0.353 mass% or less (ratio relative to the charged amount), 0.201g of methanol was added, and the components were reacted at a liquid temperature of 70℃for 60 minutes. When the residual isocyanate group concentration becomes 0.0500 mass% or less, the reaction is terminated.
The urethane oligomer obtained is shown in Table 2Three urethane oligomers "HT- (PPG 2000-T" shown in comparative example 3) 3 -H”、“HT-(PPG2000-T) 3 -S-(CH 2 ) 3 -Si(OMe) 3 "He" HT- (PPG 2000-T) 3 Mixtures of OMe ".
Comparative Synthesis example 6
Synthesis example 3 of urethane acrylate not corresponding to component (A)
A reaction vessel equipped with a stirrer was charged with 65.4g of polypropylene glycol having a number average molecular weight of 2,000, 7.60g of 2, 4-toluene diisocyanate and 0.0180g of 2, 6-di-t-butyl-p-cresol, respectively, and these components were heated while stirring until the liquid temperature reached 40 ℃. Next, after 0.0200g of dibutyltin dilaurate was added, the liquid temperature was raised to 60 ℃ over 10 minutes while stirring. Thereafter, each component was stirred for 60 minutes, and after the residual isocyanate group concentration became 1.25 mass% (ratio with respect to the charged amount) or less, 0.0280g of gamma-mercaptopropyl trimethoxysilane and 1.72g of 2-hydroxyethyl acrylate were added, and each component was reacted at a liquid temperature of 70℃for 90 minutes. After the residual isocyanate group concentration became 0.386 mass% (relative to the charged amount) or less, 0.220g of methanol was added, and the components were reacted at a liquid temperature of 70℃for 60 minutes. When the residual isocyanate group concentration becomes 0.0500 mass% or less, the reaction is terminated.
The urethane oligomers obtained were three urethane oligomers "HT- (PPG 2000-T" shown in comparative example 4 in Table 2 3 -H”、“HT-(PPG2000-T) 3 -S-(CH 2 ) 3 -Si(OMe) 3 "He" HT- (PPG 2000-T) 3 Mixtures of OMe ".
Table 1 shows the changes in the formulation when synthesizing urethane oligomer mixtures, wherein the content of gamma-aminopropyl triethoxysilane terminated urethane acrylate oligomer is different from synthesis examples 1 to 3 described above. The synthesis examples shown in Table 1 correspond to "HT- (PPG 2000-T) used in examples 1 to 7 and comparative example 1 in Table 2 in order from top to bottom 3 -H”、“HT-(PPG2000-T) 3 -S-(CH 2 ) 3 -Si(OMe) 3 "He" HT- (PPG 2000-T) 3 OMe "urethane oligomer mixture.
TABLE 1
Formulation changes when synthesized with different gamma-aminopropyl triethoxysilane end-capped urethane acrylate oligomer content
The abbreviations in table 1 have the following meanings.
PPG: polypropylene glycol with number average molecular weight of 2,000
TDI:2, 4-toluene diisocyanate
gamma-APTES: gamma-aminopropyl triethoxysilane
MeOH: methanol
NCO% (1): the residual isocyanate group concentration after the PPG and TDI reactions, indicative of the reference value at the time of synthesis
NCO% (2): residual isocyanate group concentration after reaction of gamma-aminopropyl triethoxysilane with HEA, indicating reference value at synthesis
Evaluation method
(1) Viscosity:
the viscosity at 25℃of the compositions obtained in examples and comparative examples was measured according to JIS K6833-1 and JIS K7117-1 using a TVB-10H viscometer (manufactured by TOKI SANGYO CO., LTD.).
(2) Young's modulus:
young's modulus of cured products obtained by curing the compositions obtained in examples and comparative examples was measured. The test film was obtained by: the liquid curable resin composition was applied to a glass plate using an application bar having a thickness of 381 μm by applying an energy of 1J/cm in air 2 To cure the resin composition and then peeling the composition from the glass plate. These cured films were allowed to stand at a temperature of 23℃and a relative humidity of 50% for a prescribed period of time, and then prepared to have a width of 6mm and a lengthStrip samples of 25 mm. These tape-like samples were subjected to tensile test under the same temperature and relative humidity conditions using a 5542C4600 tensile tester (manufactured by Instron Japan co., ltd.) according to JIS K7161-1. Young's modulus is determined by the tensile strength at a traction speed of 1mm/min and a strain of 2.5%.
(3) Glass bond strength:
the glass adhesion strength of the cured product obtained by curing the compositions obtained in examples and comparative examples was measured. The test film was obtained by: the liquid curable resin composition was applied to a glass plate using an application bar having a thickness of 381 μm and was cured by applying an energy of 1J/cm in air 2 To cure the resin composition. These cured films were left to stand at a temperature of 23℃and a relative humidity of 50% for a prescribed period of time, and then prepared into a bar-shaped sample having a stretched portion having a width of 10mm and a length of 50 mm. These tape-like samples were subjected to glass adhesion strength test under the same temperature and relative humidity conditions using a 5542C4600 tensile tester (manufactured by Instron Japan co., ltd.) in accordance with JIS Z0237. The glass bond strength was determined after 30 seconds from the tensile strength at a draw speed of 50 mm/min.
The results obtained by the above evaluation are shown in tables 2 and 3 below.
The terminal structures of the oligomers shown in Table 2 are shown below.
Formula (III) NH-CO-S- (CH) 2 ) 3 -Si(OMe) 3
Formula (IV) NH-CO-NH- (CH) 2 ) 3 -Si(OMe) 3
Formula (V): -NH-CO-NH- (CH) 2 ) 3 -Si(OEt) 3
In the above formulas (III), (IV) and (V), "Me" is a methyl group, "Et" is an ethyl group, and "×" represents a bond.
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Claims (28)
1. A composition for forming a coating layer of an optical fiber, the composition comprising a compound having a structure represented by the following formula (I):
(I)*-NH-CO-N(R 1 )-R 2 -SiR 3 n -(OR 4 ) 3-n
wherein R is 1 Is a hydrogen atom, an alkyl group or an aryl group, R 2 C is a methylene group optionally substituted with halogen, a radical which may have a heteroatom or contain a heteroatom between carbon atoms, and optionally substituted with halogen 2-10 An alkylene group, or a phenylene group which may have a substituent, R 3 Is an alkyl group, and R 4 Is C 1-6 Alkyl groups, are bonds and n represents an integer of 0 or more and an integer of 2 or less.
2. The composition for forming a coating layer of an optical fiber according to claim 1, wherein R 1 Is a hydrogen atom or C 1-10 An alkyl group.
3. The composition for forming a coating layer of an optical fiber according to claim 1 or 2, wherein R 2 C being a radical which may have heteroatoms or contain heteroatoms between carbon atoms 2-10 An alkylene group.
4. A composition for forming a coating layer of an optical fiber according to any one of claims 1 to 3, wherein the hetero atom or hetero atom-containing atomic group is selected from NH, O and S.
5. The composition for forming a coating layer of an optical fiber according to any one of claims 1 to 4, wherein R 3 Is C 1-10 An alkyl group.
6. According to claim1 to 5, wherein R is 4 Is C 2-6 An alkyl group.
7. The composition for forming a coating layer of an optical fiber according to any one of claims 1 to 6, wherein the content of the compound having the structure represented by formula (I) is 0.05 parts by mass or more and less than 4.5 parts by mass per 100 parts by mass of the composition.
8. The composition for forming a coating layer of an optical fiber according to claim 7, wherein the content of the compound having the structure represented by formula (I) is 0.4 parts by mass or more and less than 3 parts by mass per 100 parts by mass of the composition.
9. The composition for forming a coating layer of an optical fiber according to any one of claims 1 to 8, wherein the compound having a structure represented by formula (I) is a urethane (meth) acrylate oligomer.
10. The composition for forming a coating layer of an optical fiber according to claim 9, wherein the urethane (meth) acrylate oligomer comprises a single (meth) acrylate group.
11. The composition for forming a coating layer of an optical fiber according to any one of claims 1 to 10, further comprising a photopolymerization initiator.
12. The composition for forming a coating layer of an optical fiber according to any one of claims 1 to 11, further comprising a reactive diluent monomer.
13. A cured layer formed from the composition for forming a coating layer of an optical fiber according to any one of claims 1 to 12.
14. An optical fiber having the cured layer of claim 13.
15. A fiber optic ribbon or cable comprising two or more optical fibers according to claim 14.
16. Use of a composition comprising a compound having a structure represented by the following formula (I):
(I)*-NH-CO-N(R 1 )-R 2 -SiR 3 n -(OR 4 ) 3-n
wherein R is 1 Is a hydrogen atom, an alkyl group or an aryl group, R 2 C is a methylene group optionally substituted with halogen, an atomic group which may have a heteroatom between carbon atoms or a heteroatom, and may be optionally substituted with halogen 2-10 An alkylene group, or a phenylene group which may have a substituent, R 3 Is an alkyl group, and R 4 Is C 1-6 Alkyl groups, are bonds and n represents an integer of 0 or more and an integer of 2 or less.
17. The use according to claim 16, wherein R 1 Is a hydrogen atom or C 1-10 An alkyl group.
18. The use according to claim 16 or 17, wherein R 2 C being a radical which may have heteroatoms or contain heteroatoms between carbon atoms 2-10 An alkylene group.
19. The use according to any one of claims 16 to 18, wherein the heteroatom or heteroatom-containing radical is selected from NH, O and S.
20. The use according to any one of claims 16 to 19, wherein R 3 Is C 1-10 An alkyl group.
21. The use according to any one of claims 16 to 20, wherein R 4 Is C 2-6 An alkyl group.
22. The use according to any one of claims 16 to 21, wherein the content of the compound having the structure represented by formula (I) is 0.05 parts by mass or more and less than 4.5 parts by mass per 100 parts by mass of the composition.
23. The use according to claim 22, wherein the content of the compound having the structure represented by formula (I) is 0.4 parts by mass or more and less than 3 parts by mass per 100 parts by mass of the composition.
24. The use according to any one of claims 16 to 23, wherein the compound having the structure of formula (I) is a urethane (meth) acrylate oligomer.
25. The use of any one of claims 16 to 24, wherein the urethane (meth) acrylate oligomer comprises a single (meth) acrylate group.
26. The use according to any one of claims 16 to 25, further comprising a photopolymerization initiator.
27. The use of any one of claims 16 to 26, further comprising a reactive diluent monomer.
28. A method for producing an optical fiber, the method comprising:
Disposing the composition according to any one of claims 1 to 12 on at least a portion of a surface of a glass fiber; and
the composition is cured to form a coating layer.
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JP2020-192249 | 2020-11-19 | ||
JP2021053354A JP2022081377A (en) | 2020-11-19 | 2021-03-26 | Optical fiber coating layer forming composition and cured layer, thereof as well as optical fiber with cured layer and use of optical fiber coating layer forming composition |
JP2021-053354 | 2021-03-26 | ||
PCT/JP2021/042243 WO2022107811A1 (en) | 2020-11-19 | 2021-11-17 | Composition for forming coating layer of optical fiber and cured layer thereof, optical fiber having cured layer, and use thereof |
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CN116529220A true CN116529220A (en) | 2023-08-01 |
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